Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
  • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
  • C08F290/04—Polymers provided for in subclasses C08C or C08F
  • C08F290/046—Polymers of unsaturated carboxylic acids or derivatives thereof
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F259/00—Macromolecular compounds obtained by polymerising monomers on to polymers of halogen containing monomers as defined in group C08F14/00
  • C08F259/08—Macromolecular compounds obtained by polymerising monomers on to polymers of halogen containing monomers as defined in group C08F14/00 on to polymers containing fluorine

Definitions

• the present invention relates to a fluorine-containing graft copolymer and its manufacturing method.
• the fluorine-containing graft copolymer is synthesized by copolymerization of a monomer with perfluoroalkyl group and a macromonomer that has copolymerizable vinyl group at one end of a molecule.
• the graft copolymer consists of the perfluoroalkyl lo compound and macromonomer segment as a backbone and branched chains, respectively. Since the graft copolymer has miscibility with the substrates for surface modification, various applications are expected in the field of water/oil repellent, soil release agents, mold release agents, etc.
• Fluorine-containing copolymers obtained by copolymerization of the perfluoroalkyl compound with other copolymerizable vinyl monomers, have been known to be very useful as low-energy surface modifiers in various forms hitherto. But it is known that perfluoroalkyl compounds show poor adhesiveness due to the extremely low-energy surface characteristics with various substrates like fiber, plastic, rubber, ceramic and metal etc.
• the perfluoroalkyl compound and comonomers are resided in the backbone concurrently, thus show the mixed surface properties of the two monomers; Namely, the low-energy modification characteristics from the perfluoroalkyl compound is damaged by high surface energy comonomer, and the surface modification effect of the copolymer is reduced. Therefore, when the random copolymer is used tor low-energy, surface modification of substrates, excessive amounts of high-priced perfluoroalkyl compound should be used in order to reduce the surface energy of the substrate to the desired level. And manufacturing costs of the random copolymer are deemed to be high compared with the performances.
• a graft type copolymer was synthesized using oligomer of perfluoroalkyl compound as branched chains and other comonomers as a backbone by solution or emulsion polymerization. And the graft copolymers have been used as a fluorine-containing surface modifier (Japanese Patent unexamined publication Soh 54-137489 and Soh 56-163183).
• the homopolymer of perfluoroalkyl compound as a branched chain has lower degree of polymerization, its mechanical properties may be suspected.
• the fluorine-containing graft copolymer is synthesized the emulsion copolymerization of a perfluoroalkyl compound and a macromonomer that has only high molecular weight perfluorinated segments in the backbone and shows an affinity of a branched chain to the substrates, respectively.
• the object of present invention is to provide the fluorine-containing graft copolymer and its manufacturing method having better low-energy surface modification properties and superior compatibility with the substrates compared with random copolymers or graft copolymers with a oligomer of perfluoroalkyl compound as mentioned above which have been used largely as a surface modifier at present.
• the present invention relates to a graft copolymer for a surface modifier comprising the perfluoroalkyl compound selected from the following chemical formulas (1), (2), (3) and (4) as a backbone with macromonomers from the monomers of unsaturated double bond as branched chains.
• R 1 is hydrogen, or methyl group
• R 2 is methyl, ethyl, or propyl group
• X is hydrogen, fluorine, or chlorine
• n is an integer of 2 to 6 and
• n is an integer of 3 to 21
• the fluorine-containing graft copolymer of the present invention since the branched chain is consisted of the macromonomers having the same chemical structure as substrates, it is miscible with substrates. Further, the backbone of the graft copolymer is composed of only perfluoroalkyl compound. Hence, the graft copolymer shows a remarkable low-energy Surface modification effect due to the superior surface migration activity of the fluorinated segment and air-side orientation of perfluoroalkyl group.
• the macromonomers which composed of branched chains are made by anionic or radical polymerization using the comonomers having unsaturated double bonds.
• the available comonomers in the present invention includes one or more than selected from following vinyl monomers e.g., (meth)acrylic acid, methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, hexyl (meth)acrylate, dodecyl (meth)acrylate, stearyl (meth)acrylate, benzyl (meth)acrylate, cyclohexyl (meth)acrylate, acrylonitrile, acrylamide, vinyl acetate and styrene; and monomers containing the crosslinkable group e.g., N-methylol (meth) acrylamide, N-methylol acrylamide butylether, N-butoxy (meth)acrylamide, 2-hydroxy (meth)acrylate, and 2-hydroxypropyl (meth)acrylate.
• vinyl monomers e.g., (meth)acrylic acid, methyl (meth)acrylate, e
• a macromonomer is synthesized first by polymerizing the above mentioned monomers or comonomers comonomers for branched chains and then, copolymerized with perfluoroalkyl compound, expressed as chemical formulas (1) to (4), by the solution or emulsion polymerization.
• some emulsifying solvent may be added so as to improve its emulsion property according to the types of comonomers.
• the solvent for emulsion may be typically selected from one or more following solvents, for examples, ketones such as acetone, methylethylketone, etc.; hydrocarbon halides such as carbon tetrachloride, chloroform, benzotrifluoride, 1,1,2-trichlorotrifluoroethane, etc.; acetates such as ethyl acetate, butyl acetate etc.; aromatic hydrocarbons such as benzene, toluene, xylene, etc.; tetrahydrofuran; and dimethylformaldehyde.
• concentration in 15 ⁇ 30% by weight is preferable, in general. Emulsion and solution polymerizations are carried out either at normal or at elevated pressure
• the graft copolymer that synthesized by forementioned method consist of the perfluoroalkyl compound as a backbone and macromonomer from monomers or comonomers as branched chains, and their weight ratio has a range of 5/95 to 95/5.
• its compatibility with substrates for the surface modification proves to be quite excellent with the remarkable low-energy surface modifiction effect.
• the synthesized graft copolymer may be used directly in the form of solution and emulsion or as an additive after precipitation for a surface modifier such as water and oil repellent, etc.
• MMA methyl methacrylate
• THF tetrahydrofuran
• AIBN 2,2'-azobisisobutyronitrile
• thioglycol 4.68 g, 0.06 mol
• HTPMMA hydroxy-terminated-poly(metyl methacrylate)
• the number molecular weight of HTPMMA was 9.000 (degree of polymerization: 90) measured by gel permeate chromatography with standard poly(methyl methacrylate) (hereinafter referred to as "PMMA") after reprecipitation and drying.
• Triethyl amine (0.578 g, 5.72 mmol) was added to the reaction solution for neutralization of HCl generated, and filtrated HCl-triethylamine salt using cellite. The filtrate was added to hexane to precipitate PMMA macromonomer and dried under vacuum at room temperature. The yield of PMMA macromonomer was about 90% based on HTPMMA.
• the ratio of methyl protons of the MMA to protons from the introduced double bond of the PMMA macromonomer, so formed, was calculated by analyzing with nuclear magnetic resonance (NMR) using CDCl 3 .
• the calculation was done by obtaining the ratio of the methyl protons of MMA (at about 3.7 ppm) and introduced double bond (3 complex protons at about 5.8 to 6.4 ppm).
• FMA1 perfluoroalkylethyl methacrylate
• NP-50 polyoxyethylenenonylphenylether
• the reaction mixture was precipitated to excess methanol, and washed with hot methanol for about 48 hrs using Soxhlet extractor.
• the yield of graft copolymer was about 70%.
• R-113 ClCF 2 CCl 2 F
• the NMR analysis showed that the peak corresponding to methylene protons from FMA1 and methyl protons were observed at about 4.3 ppm and 3.7 ppm, respectively. From this results, the calculated weight ratio between FMA1 and MMA was 43/57.
• PMMA macromonomer was manufactured in the same manner as did in EXAMPLE 1; but for the manufacture of PMMA macromonomer having a molecular weight of 3,000, thioglycol (23.4 g, 0.1 mole based on MMA) was added for the synthesis of HTPMMA.
• thioglycol 23.4 g, 0.1 mole based on MMA
• HTPMMA a molecular weight of 3,000
• thioglycol 23.4 g, 0.1 mole based on MMA
• the graft copolymer was manufactured by emulsion polymerization of both PMMA macromonomer and perfluoroalkyl compound in the ratio defined in the following table 2.
• PMMA macromonomer (molecular weight: 9.000, 70 g, 7.78 mmol) so formed from said EXAMPLE 1 and FMA 1 (30 g), was added to benzotrifluoride (400 g) and dissolved completely.
• AIBN (0.15 g, 0.5% by weight based on FMA1) was added and degassed with nitrogen flow for 30 minutes. Then, the reaction solution was stirred and reaction was initiated by increasing the temperature to 70° C. After about 5 day, the conversion was about 90%.
• the graft copolymer, so synthesized, was analyzed with NMR as the same method as EXAMPLE 1 and as a results, it was noted that the weight ratio of FMA1/MMA was about 36/64.
• reaction solvents a mixture THL/R-113 or chloroform/R-113 was employed in stead of benzotrifluoride but similar results was obtained.
• the fluorine-containing surface modifier with the type of the graft copolymer manufactured by the present invention has a remarkable affinity to substrate, which is desirable properties of the two phase graft copolymer, as well as having excellent water/oil repellency, when compared with conventional random copolymers (COMPARATIVE EXAMPLE).
• the graft copolymer manufactured based on the present invention is in particular useful in the field of low-energy surface modifiers including water and oil repellents, soil release agents, anti-contaminant resin additives.

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• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Macromonomer-Based Addition Polymer (AREA)

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Citations (1)

• 1996
  • 1996-04-10 KR KR1019960010736A patent/KR100206452B1/ko not_active IP Right Cessation
  • 1996-07-26 US US09/155,905 patent/US6096827A/en not_active Expired - Fee Related
  • 1996-07-26 JP JP09536083A patent/JP2000508360A/ja active Pending
  • 1996-07-26 CA CA002250939A patent/CA2250939A1/fr not_active Abandoned
  • 1996-07-26 WO PCT/KR1996/000119 patent/WO1997038032A1/fr not_active Application Discontinuation
  • 1996-07-26 EP EP96925151A patent/EP0892821A1/fr not_active Withdrawn

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Non-Patent Citations (6)

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